Blue light blocking system containing pyrazoline or/and phenylacrylic compounds

ABSTRACT

A blue light blocking system including a pyrazoline compound of formula (I) or/and a phenylacrylic compound of formula (II) is provided. The compound of formula (I) or formula (II) can absorb most blue light of shorter wavelength that hurt eyes, but let that of the longer wavelength pass through, so that the transmitted light makes an excellent visual effect for human. The system can be applied to products such as optical films, optical lenses, goggles, skin care, lighting, coatings, adhesives, or panels. These products have a light-colored appearance and their transmitted light makes for an excellent visual effect.

FIELD

The present invention relates to a blue light blocking system, involvinga blue light blocking composition or a blue light blocking film. Theblue light blocking film is made from blue light blocking composition.The blue light blocking composition or blue light blocking film includesnovel blue light blocking agents, which can absorb most blue light ofshorter wavelength that hurt eyes, but let the longer wavelength bluelight pass through, so that the transmitted light makes an excellentvisual effect. The compounds of the invention have advantages, inparticular, of a light-colored appearance. They selectively absorb bluelight and can be used in areas such as optical films, optical lenses,goggles, skin care, lighting, coatings, adhesives or panels.

BACKGROUND

Visible light includes red, orange, yellow, green, blue, indigo, andpurple light. Red light has the longest wavelength and purple light hasthe shortest, and the shorter of the wavelength, the higher of theenergy. Blue light can cause free radicals in the body (InvestigativeOphthalmology & Visual Science (20140731), 55 (7), pp. 4119-4127). Theblue light emitted from the 3C screen can easily pass through eye lensin the dim, which may cause ciliary muscle spasm, presbyopia, andmacular lesions after a long time exposure. At present, blue lightblocking agents are mainly dyes and inorganic phosphor compounds. Darkcolor is one of the disadvantages of these agents. For example,brown-colored glasses (CN106466925, CAPLUS AN 2017: 351046) are notsuitable for indoor use.

A good blue light blocking agent must have at least two basicrequirements. First, it can filter blue light. Second, it has a lightcolor. In addition, an excellent blue light blocking agent is requiredto absorb blue light selectively, because the non-selective absorptionof all bands of blue light can cause a visually unnatural feeling. Inhigh-end applications, the absorption needs to gradually decrease as thewavelength increases, that is, blue light of longer wavelengths musthave greater penetration. For example, for the optical lens, thetransmitted blue light needs to have a 50% to 100% increasingpenetration from 410 nm to 450 nm. In this way, it can cause a bettervisual feeling. Therefore, the conditions for being a blue lightblocking agent are very severe. Actually there are few products on themarket that can meet above requirements.

There has been disclosed a compound of formula (II-5) having a structurevery similar to that of the compound of formula (II-1) of the presentinvention. The compound of formula (II-5) is dimethyl(p-methoxybenzylidene) malonate (trade name Eusorb-1988 or Clarianthostavin pr 25).

Compound of formula (II-5) has a maximum absorption peak at 314 nm, andis widely used as UVB (290-320 nm) ultraviolet absorbers (JP 4822129,CAPLUS AN 2008: 1039270) without blue light blocking effect (see alsoTable 1 of the present invention).

Compound of formula (II-1) of the present invention, has been disclosedin US2004126700 (Table 1, EC13) but the maximum absorption is indicatedas 338-339 nm (much below 380 nm).

Therefore, both OCH3 or N(CH3) 2 substituted dimethyl2-benzylidenemalonate (II-1 or II-5) has not been used or disclosed orconsidered for blue light blocking in the prior art teaching.

There has been disclosed a compound of formula (II-7) having a structurevery similar to that of the compound of formula (II-2) of the presentinvention.

Compound of formula (II-7) has a maximum absorption peak at 340 nm andis applied to ultraviolet absorbers. For example, claim 1 of JP09221583(CAPLUS AN 1997: 571294) and U.S. Pat. No. 4,284,621 (CAPLUS AN 1980:116437) both disclose applications in UVA absorption.

The use of the compound of formula (II-2) is known as a photoinitiatorand was disclosed in J. App. Polym. Sci. Photosensitive resinscontaining p-dimethyl-aminobenzylidene derivatives and diphenyliodoniumsalt as photoinitiators, 1987, 34 (8), p. 2747-56 or JP03062163B (CAPLUSAN 1986: 79233). Its role is to cause free radicals to produce a seriesof photochemical chain reactions. This effect is completely differentfrom the protecting effect for organism of the blue light blockingagents in present invention. Actually, the function for blue lightblocking of the claimed compounds have never been applied, disclosed orpredicted in the prior arts.

The pyrazoline compounds of formula (I) of the present invention areoriginally used as a photoinitiator in a photoresist for a printedcircuit board, or as a reflective whitening agent in the opaquefiber-reinforced resin layer of the charge transport material printedcircuit board, or as a charge transfer agent in the field ofelectrophotography, or as an antibacterial agent. For example, page 10of CN102012634A (or column 4 of U.S. Pat. No. 8,198,008B2) disclosescompound (I-1) as a photoinitiator, U.S. Pat. No. 8,361,697 disclosescompound (I-1) as a high-sensitivity photoinitiator at h-line (405 nm),JP 63033481 (CAPLUS) AN 1981: 10007) discloses compounds (I-2) or (I-3)as photoinitiators.

For another example, (I-2) and (I-3) have been disclosed antibacterialeffects in Chemical & Pharmaceutical Bulletin, 46 (8), 1998, p.1254.Above disclosed functions have nothing to do with the filtering orprotection function of the blue light blocking agent of the presentinvention, and have never been applied or disclosed for the blue lightblocking function.

SUMMARY

For a good blue light blocking agent, function of filtering blue lightand good color appearance are two basic requirements. For an excellentagent, it is required for further absorption capacity for the assignedblue light bands, so that the transmitted light can provide an excellentvisual effect. Thus, the conditions for being an excellent blue lightblocking agent are very severe.

To achieve this goal, the present invention specifically designs andscreens for blue light blocking compounds. Surprisingly, the inventorshave successfully devised compounds of formula (I) and (II), which canbe used as excellent blue light blocking agents. The inventors alsodesigns a blue light blocking system using (I) or (II) alone or incombination. The invention overcomes the disadvantages of traditionalblue light blocking agents. For example, it overcomes the shortcomingsof the dark colors caused by traditional dyes or inorganic phosphoragents. For another example, it overcomes the shortcomings oftraditional blue light blocking agents that excessively absorblong-wavelength blue light, which causes poor visual experience.

The basic design of the blue light blocking agent system of the presentinvention is to use the blue light blocking compound of formula (I)alone or the formula (II) alone. Because at about 400±20 nm, there is amaximum absorption peak for formula (I) or formula (II). The blue lightblocking compounds can also be used in combination, for example, acombination between three analogs of formula (I-1), formula (I-2), andformula (I-3), or, for another example, a combination between twoanalogs, formula (II-1) and formula (II-2). The advantage is that, onthe one hand, the analogs in between have good compatibility, and on theother hand, by adjusting the ratio between the analogs, it canselectively absorb blue light in different bands, making the transmittedblue light better visual effect.

The maximum absorptions of (I-1), (I-2), and (I-3) in the blue regionare each about 390 nm, 380 nm, and 420 nm, respectively (slightlydifferent in different solvents). Mixing at a specific ratio can achievedifferent effects through filtering blue light. Compound (I-1), (I-2),and (I-3) have similar structures, therefore can be well mixed insolvents with almost any ratio. In this way, by controlling the ratio of(I-1), (I-2), and (I-3) compounds, blue light in different wavelengthbands can be selectively absorbed, so that the transmitted blue lightcan provide good visual effect. In the same way, the blue light blockingagent system can also be a combination of compounds of formula (II),such as a combination of compounds of formula (II-1) and formula (II-2).

The maximum blue light absorption of compounds of formula (II-1) and(II-2) is about 380 nm, 420 nm (slightly different in differentsolvents). By controlling the ratio of (II-1) and (II-2), the blue lightcan be selectively absorbed, so that the transmitted blue light canprovide a better visual effect.

The blue light blocking system can also be a combination of compounds offormula (I) and formula (II), for example, the combinations selectedfrom compound of formula (I-1), formula (I-2), formula (I-3), formula(II-1), and formula (II-2).

Compounds of formula (I-1), formula (I-2), formula (I-3), formula(II-1), formula (II-2) have maximum absorption peaks at about 400±20 nm,and all of which can effectively removes the harmful blue light, ie.,the blue light with shorter wavelengths.

From wavelength of 410 nm to 450 nm, the absorption of (I-1), (I-2),(I-3), (II-1), and (II-2) compound, decrease linearly (or close tolinearly). These result in the transmitted blue light provide goodvisual effect for human. Although the structures of the compounds offormula (I) and (II) are not similar, many solvents can be used for bothcompounds of formula (I) and (II), for example, toluene, methyl ethylketone, isopropyl alcohol, ethyl acetate, acetonitrile, and the like.Therefore, the compounds of formula (I) and (II) can be mixed in solventor solvent combination with various proportions to achieve the effect ofblue light blocking.

The blue light blocking system can be used in combination withultraviolet blocking compounds to achieve functions of preventing bothultraviolet and blue light at the same time. For example, dimethyl(p-methoxybenzylidene) malonate (that is, compound of formula II-5, UVabsorption maximum absorption peak at 314 nm),2,2′-(1,4-benzenedimethylene) tetraethyl dimalonate (i.e. compound offormula II-6, UV absorption maximum absorption peak at 320 nm), andcyano-p-methoxycinnamate (i.e. compound of formula II-7, UV absorptionmaximum absorption peak at 340 nm).

UVA (approximately 320-400 nm) ultraviolet light can penetrate glass. Itis the main ultraviolet light in rooms. In contrast, UVB (about 290-320nm) ultraviolet light is the main ultraviolet light of solar radiationthat causes biological effects on skin outdoors.

In many applications, it is expected to absorb both UVA (about 320-400nm) and blue light (about 380 nm-450 nm) at the same time. Other bluelight blocking systems that absorb both UVAB (about 290-400 nm) andfull-band blue light (about 380 nm-450 nm) are also expected.

Blue light with a wavelength of 410 nm-450 nm is a low-energy bluelight. A blue light blocking system with decreasing absorption valuesfrom wavelength of 410 nm to 450 nm is expected, because the resultingpenetrating light can provide a good visual effect. An UV-blue lightblocking system with UVAB absorption (about 290-400 nm) and selectiveabsorption of blue light (from 410 nm to 450 nm with decreasingabsorption) is highly anticipated. For example, a specific combinationof one or more compounds selected from formula (I-1), formula (I-2),formula (I-3), formula (II-1), formula (II-2), formula (II-5), formula(II-6), and formula (II-7).

Compounds of Present Invention:

Wherein, R₁ to R₃ are each independently selected from H, straight orbranched C₁ to C₆ alkyl, OR₃, and N(R₃)₂, and R₄ to R₆ are eachindependently selected from H, and straight or branched C₁ to C₆ alkyl,R₇ to R₈ are each independently selected from COOR₉, CONR₁₀R₁₁, COR₁₂,and CN, and R₉ is selected from H, straight or branched C₁ to C₁₈ alkyl,and polyethylene glycol groups, and R₁₀ to R₁₂ are each independentlyselected from H, straight or branched C₁-C₆ alkyl, and phenyl.

A preferred embodiment, R₁ to R₂ are each independently selected from C₁to C₅ alkyl, OCH₃, and N (CH₃)₂, R₃ to R₄ are H, and R₅ to R₆ are eachindependently linear or branched C₁ to C₄ alkyl, R₇ to R₈ are eachindependently selected from COOR₉, CONR₁₀R₁₁, COR₁₂, and CN, R₉ is H ora linear or branched C₁ to C₁₈ alkyl group or a polyethylene glycolgroup with a molecular weight of 40 to 500, R₁₀ to R₁₂ each isindependently selected from H, straight-chain or branched C₁-C₄ alkyl,and phenyl.

More preferably, R₁ to R₂ are each independently selected fromtert-butyl, methoxy, and dimethylamino groups, R₃ to R₄ are H, and R₅ toR₆ are each independently linear or branched C₁ to C₄ alkyl groups, R₇to R₈ are each independently selected from COOR₉ and CN, and R₉ is alinear or branched C₁ to C₄ alkyl group or a polyethylene glycol grouphaving a molecular weight of 40 to 350.

Particularly preferred embodiments include compounds of formula (I-1),formula (I-2), formula (I-3), formula (II-1) and formula (II-2).

A particularly preferred embodiment further includes a combination ofone or more compounds of (I-1), (I-2), (I-3), (II-1), and (II-2).Another particularly preferred embodiment includes one or more compoundsin combination selected from, for example, compounds of formula (I-1),formula (I-2), formula (I-3), formula (II-1), formula (II-2), formula(II-5), formula (II-6) and formula (II-7). Among them, formula (II-5),formula (II-6), and formula (II-7) are UV blocking compounds.

The UV blocking compounds can be dimethyl (p-methoxybenzylidene)malonate (compound of formula II-5), 2,2′-(1,4-benzenedimethylene)dimalonate Ethyl ester (compound of formula II-6),cyano-p-methoxycinnamate (compound of formula II-7),(2-benzotriazol-2-yl)-4,6-bis (1-methyl 1-phenylethyl) phenol,2,2′-methylenebis (4-tert-octyl-6-benzotriazolephenol), or other UVblocking compounds.

The substituents of polyethylene glycol and fatty ester of the compoundof formula (II) of the present invention have excellent low migrationand high compatibility in application. In addition, the phenylacryliccompound of formula (II) according to the present invention can reactwith various resins, monomers or prepolymers to achieve the advantagesof low mobility and high compatibility.

The blue light composition of the present invention can be optionallyadded a free radical scavenger or an antioxidant or a polymerizationinhibitor, so that an unexpected light reaction is prevented while instoring. In addition, adjusting the pH of the composition can alsoprevent unexpected photoreactions. In the polymerization reaction of theblue light blocking composition, the selection of an appropriatewavelength initiator can also avoid the occurrence of unexpected lightreactions.

As mentioned above, the prior arts disclose the photo-initiating effectof compounds of formula (I) or formula (II) on photoresists of printedcircuit boards. Their function is to cause free radicals to produce aseries of photochemical reactions. This function is a destructiveeffect, and is completely different from the protection function of theblue light blocking agents of the present invention. In addition, theapplication of the blue light blocking system of the present inventionis to filter out bad blue light. On the one hand, the transmitted lightdoes not have short-wavelength blue light that is harmful to the humanbody. On the other hand, visible light other than short-wavelength bluelight can still pass through. This is completely different from thefunction of reflecting to block light of the fiber-reinforced resin ofthe opaque layer in the printed circuit board. Furthermore, the chargetransfer functions and the blue light blocking system of the presentinvention are completely different.

Synthesis Route of Compounds of Formula (I-1) (Example 1):

Synthesis Route of Compounds of Formula (II-1) (Example 4):

The basic structure of the blue light blocking system of the presentinvention includes one or more blue light blocking film layers. The bluelight blocking film layer can apply on article directly or put on abasal layer. The blue light blocking system can further have a releaselayer or release layers. Basically, the blue light blocking compositioncan apply on a basal layer or a release layer and then dried.Alternatively, a transfer coating process is to coat the composition onthe release film and then transfer it to the basal layer. When the upperand lower layers of the blue light blocking film are laminated with arelease film, this is called OCA optical clear adhesive (Optically ClearAdhesive).

Coating methods are conventional techniques, including traditional brushcoating, spray coating, curtain coating, roll coating, slit coating, airknife coating, blade coating, and metering rod coating. Drying methodsinclude natural drying, microwave drying, ultraviolet drying, infrareddrying, and hot air drying.

The basal layer includes one or more of material, such as polyester,glass, polyethylene, polypropylene, polycarbonate, polyamide,polyacrylate, polymethacrylate, polyvinyl acetate, and polyvinylchloride. The release film material includes silicone and non-silicone.Non-silicone material includes, for example, one or more mixtures ofpolyethylene, polypropylene, polyurea, polyacrylic, polyester, andfluorocarbons. OCA optical glue can be applied to different fieldsaccording to different thicknesses, such as transparent device binding,display assembly, lens assembly, panel, glasses or polycarbonate plasticmaterials.

The blue light blocking film may also include other film layers, such asa UV absorbing film layer, an anti-fog film layer, and an antistaticfilm layer. Blue light blocking film can be used in the optical orelectronic industry, such as optical lenses, goggles, lenses, displays,panels, light protection.

The thermal initiation blue light blocking composition usually includesblue light blocking agent, a thermal initiator, a monomer, a solvent,and an auxiliary agent. Thermal initiators are classified according tothe initiation temperature. High temperature (above 100° C.) initiatorscan be selected from alkyl peroxides, alkyl hydrogen peroxide compounds,and peroxide ester compounds. Medium temperature (40-100° C.) initiatorsinclude azo compounds, diacyl peroxide, or persulfate, etc. Lowtemperature (0-40° C.) initiators, for example, are used in redoxinitiation system. Thermal initiators can be divided into azo compoundsand peroxides according to their molecular structure. The common usedazo compounds include azobisisobutyronitrile (ABIN),azobisisoheptonitrile (ABVN), and azo compounds with carboxyl orsulfonic acid groups. The common used peroxides include benzoyl peroxide(BPO), di (2,4-dichlorobenzoyl) peroxide, diacetyl peroxide, dioctanoylperoxide, dilauroyl peroxide, and diisopropyl peroxide. Benzene peroxide(DCP), di-tert-butyl peroxide (DTBP), tert-butyl peroxide benzoate(BPB), cumene hydrogen peroxide (CHP), tert-butyl hydrogen peroxide(TBH), Diisopropyl peroxide (IPP), diisobutyl peroxide (IBP),dicarbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide,persulfate and hydrogen peroxide.

Monomer is small molecule containing double bonds or other reactivefunctional groups. Double bond monomers include acrylic, acrylate,methacrylic, methacrylate, hydroxyacrylate, methacrylate, diacetoneacrylamide, vinyl, styrene, ethylene, vinyl fluoride, vinyl chloride,acrylonitrile, and vinyl acetate, silicone acrylate, epoxy acrylate, andpolyurethane acrylate. Acrylic or acrylate monomers include acrylatesoft monomers, acrylate hard monomers, acrylic functional monomers, orcrosslinking monomers. Preferred acrylate soft monomers are, forexample, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, oriso-octyl acrylate. Preferred acrylic hard monomers are, for example,methyl acrylate and methyl methacrylate. Preferred acrylic functionalmonomers are, for example, acrylic acid and methacrylic acid. Preferredcrosslinking monomers are, for example, hydroxyethyl acrylate,hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropylmethacrylate, and adipic acid dihydrazide (ADH).

Thermosetting resins used in blue light blocking films are, for example,polyurethane resins, epoxy resins, phenolic resins, polyurea resins,unsaturated polyester resins, or alkyd resins. The monomers can beisocyanate, epichlorohydrin, phenol, aldehyde, polyol, fatty acid,polyacid, acid anhydride, polythiol, polyamine, alcoholamine, orthiolamine. Solvents include acetonitrile, acetone, methyl ethyl ketone,cyclohexanone, benzene, toluene, xylene, ethyl acetate, butyl acetate,methyl isobutyl ketone, methanol, ethanol, isopropanol, butanol,ethylene glycol, Propylene glycol, butanediol, vinyl chloride,dichloromethane, chloroform, carbon disulfide, tetrahydrofuran,dimethylformamide (DMF), and polyethylene glycol methyl ether (EGMME).

Polyurethane is produced by the reaction of polyester polyol orpolyether polyol with isocyanate. Specifically, for example, a polyoland an isocyanate, a chain extender, and a catalyst (such asdimethylaminocyclohexane) are mixed, and then injected into a mold forcuring. Or, isocyanate and polyol react first to form a prepolymer, andthen add a chain extender. The epoxy resin monomer is formed by thereaction of epichlorohydrin and bisphenol A. Specific embodimentsinclude reacting bisphenol A with epichlorohydrin, and then adding ahardener, such as dicyandiamide (Dicy) or adipic acid dihydrazide (ADH),and an accelerator, 2-methylimidazole. The monomers of the alkyd resininclude polyols and fatty acids. Specifically, for example, glycerin,isophthalic anhydride, and fatty acids are put into a reaction tank, andheated to 200-250° C. until the desired viscosity and acid value.

The unsaturated polyester resin is a linear polymer compound having anester bond and an unsaturated double bond. Monomers include unsaturateddibasic acids and unsaturated diols, or saturated dibasic acids andunsaturated diols. In a specific embodiment, for example, propyleneglycol, butadiene anhydride, and phthalic anhydride are subjected to acondensation polymerization reaction in a reaction tank. The resultingunsaturated polyester is added with a styrene monomer to become aviscous resin, and cyclohexanone peroxide is added while in use.

Auxiliaries include one or more agents selected from stabilizers,coupling agents, leveling agents, defoamers, dispersants, solvents,chain transfer agents, catalysts, tougheners, tackifiers, plasticizers,thickeners, diluents, flame retardants, polymerization inhibitors,preservatives, hardeners, and acid-base adjusting agents.

The common used chain transfer agents are, such as aliphatic thiols anddodecyl thiols. The common used stabilizers are UV absorbers, hinderedamines, antioxidants, anti-hydrolysis agents, peroxide scavengers, freeradical scavengers. Thermally initiated blue light blocking compositionmay include blue light blocking agent mass content from 0.01% to 20%,initiator mass content from 0.01 to 10%, monomer or prepolymer orpolymer content from 50 to 99.98%, and auxiliary mass content from 0 to80%. Among them, the mass content of the blue light blocking agent ispreferably 0.05% to 10%, and more preferably 0.1% to 5%. For example, anacrylic soft monomer, an acrylic hard monomer, an acrylic functionalmonomer, and an acrylic crosslinking monomer are mixed to form a monomermixture. The monomer mixture, the initiator and the solvent are thenadded to the reaction tank, and the reaction is heated. After thereaction is completed, the temperature is lowered to the roomtemperature. The product is discharged, and is evenly coated on a basallayer.

The photo-initiated blue light blocking composition usually includes ablue light blocking agent, a polymerized monomer or/and a prepolymer, aphotoinitiator, and an auxiliary agent. Photoinitiators are mainlydivided into free radical photoinitiators and cationic photoinitiators,and the radical photoinitiator is further divided into a cleavagephotoinitiator and a hydrogen abstraction photoinitiator. Cleavage typefree radical photoinitiators are mainly aryl alkyl ketones, includingone or more compounds selected from benzoin derivatives,dialkoxyacetophenones, α-hydroxyalkyl phenones, α-aminoalkyl phenones,acylphosphines, esterified oxime ketone compounds, aryl peroxyestercompounds, halomethyl aryl ketones, organic sulfur compounds, andbenzoyl esters. Hydrogen-abstracting free-radical type photoinitiators,include one or more compounds selected from active amine, benzophenone,thia anthrone anthraquinones, coumarone, camphorquinones, and, thederivatives thereof. Cationic photoinitiators, include one or morecompounds selected from diazonium salt, diaryl iodonium salt,triarylsulfonium salt, alkylsulfonium salt, iron aromatic hydrocarbonsalt, sulfonyloxyketone, and triarylsilyl ether.

Prepolymers are oligomers that contain functional groups and can befurther reacted, for example, methacrylate oligomers, acrylateoligomers, epoxy acrylate oligomers, polyurethane acrylate oligomers,silicones Acrylate oligomer, amino acrylate oligomer, carboxy acrylateoligomer, phosphate acrylate oligomer, hydroxy polyacrylate oligomer,polyester acrylate oligomer, and polyether acrylate. Prepolymer can beused alone or in a mix.

The polymerization monomer can be one or more kinds of small moleculesin an addition or condensation polymerization reaction. Among them,double bond monomers include acrylic, acrylic, methacrylic, methacrylic,hydroxyacrylic, methacrylic, diacetone acrylamide, ethylene, styrene,diene, vinyl fluoride, vinyl chloride, acrylonitrile, and vinyl acetate,silicone acrylate, epoxy acrylate, and urethane acrylate. Acrylic oracrylate monomers, include acrylate soft monomers, acrylate hardmonomers, acrylic functional monomers, and crosslinking monomers.Preferred acrylate soft monomers are, for example, ethyl acrylate, butylacrylate, 2-ethylhexyl acrylate, or isooctyl acrylate. Preferred acrylichard monomers are, for example, methyl acrylate or methyl methacrylate.Preferred acrylic functional monomers are, for example, acrylic acid ormethacrylic acid. Preferred crosslinking monomers are, for example,hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylmethacrylate, hydroxypropyl methacrylate, or adipic acid dihydrazide.Wherein, the mass content of the blue light blocking agent is 0.01% to20%, preferably 0.05% to 10%, and more preferably 0.1% to 5%.Auxiliaries may include stabilizers, coupling agents, leveling agents,defoamers, dispersants, solvents, chain transfer agents, catalysts,tougheners, tackifiers, plasticizers, thickeners, diluents, flameretardants.

Auxiliaries may include one or more agents selected from stabilizers,coupling agents, leveling agents, defoamers, dispersants, solvents,chain transfer agents, catalysts, tougheners, tackifiers, plasticizers,thickeners, diluents, flame retardants, polymerization inhibitors,preservatives, hardeners, and acid-base adjustment agents. Commonauxiliaries include coupling agents, such as silane coupling agents. Thecommon used auxiliaries may include one or more agents selected from ofUV absorbers, hindered amine, antioxidants, and free radical scavengers.

The photo-initiated blue light blocking composition includes a masscontent of the blue light agent from 0.01% to 20%, a mass content of theinitiator from 0.01 to 10%, a monomer and/or prepolymer from 5 to99.98%, and a mass content of the auxiliary agent of 0 to 95%.Preferably, the mass content of the blue light blocking agent is 0.05%to 10%, the mass content of the initiator is 0.05 to 5%, the monomerand/or prepolymer is 5 to 99.9%, and the mass content of the auxiliaryagent is 0 to 50%. Specifically, a photo-initiated blue light blockingcomposition (for example, a combination of an acrylate monomer, anacrylate prepolymer, a blue light absorber, and an initiator Photocure84) can be mixed and uniformly applied to a clean basal layer, and thenUV-cured to form a blue light blocking film.

The non-reactive blue light blocking composition includes a blue lightblocking agent, a polymer or polymers, a solvent or solvents, and/or anauxiliary agent or agents. It mainly uses the volatilization of thesolvent or other dispersion medium in the coating film to form a solidthin film. The polymer or polymers may be selected from, but not limitedto polyacrylate, polymethacrylate, polyethylene, polypropylene,polyvinyl chloride, polystyrene, polyacrylonitrile, polyethyleneterephthalate, polyethylene terephthalate succinate, polycarbonate,polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol,acrylonitrile-styrene copolymer, thermoplastic polyurethane, polyimide,cellulose, polysulfide, polyphenylene oxide, polyformaldehyde,polysulfone, polyetheretherketone, polyamide-imide, polyetherimide,polyethersulfone, and polyetherimide. The non-initiating blue lightcomposition may include a mass content of the blue light blocking agentfrom 0.01% to 20%, a polymer content from 5 to 99.99%, and a masscontent of the auxiliary agent (from 0 to 95%).

Specifically, taking polystyrene as an example, the polystyrene plasticis dried, then pulverized into small pieces, put into a mixed solvent ofxylene/ethyl acetate, and stirred until completely dissolved. Then add aplasticizer (such as di-butyl phthalate) and a blue light blocking agentto heat and stir to obtain the composition. After coating and drying toremove the solvent, a blue light blocking film is obtained. Plasticizersfor polystyrene include phthalates, diterpenes, epoxy soybean oil, octylepoxy soybean oleate, and alkylbenzene sulfonate.

The materials of blue light blocking optical lens or goggles of thepresent invention includes glass and polymer, such as polycarbonate(PC), polymethyl methacrylate (PMMA), nylon (PA), TPX(Polymethylpentene), polystyrene, diethylene glycol dialkyl carbonateresin (PEDC). The blue light blocking agent can be added to the resin ina specific proportion for co-molding. The mass content of the blue lightblocking agent is 0.01% to 20%, preferably 0.05% to 10%, and morepreferably 0.1% to 5%. The present invention can also use animpregnation process to immerse the lens in a solution containing n bluelight blocking agent. The present invention can also use a thin filmprocess to form a blue light blocking film on the lens surface. Theinvention can also adopt a transfer coating process, for example,coating on a release film first, and then transferring to an opticallens.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention is further described below with reference to thedrawings and the embodiments.

FIG. 1 shows UV-VIS absorption of the compounds (I-1) and (II-1) of thepresent invention

FIG. 2 is a schematic diagram of the side of the blue light blockingfilm: 1. the release layer, 2. the blue light blocking layer, 3. thebasal layer

FIG. 3 is a schematic diagram of the side of the blue light blocking OCAoptical adhesive (Optically Clear Adhesive): 1. a release layer, 2. ablue light blocking layer, and 3. a release layer.

DETAILED DESCRIPTION

The following is a description of specific embodiments of the presentinvention. These are not limited to these embodiments.

Example 1 Synthesis of a Compound of Formula (I-1),1-phenyl-3-(4-butylstyryl)-5-(4-tert-butylphenyl) pyrazoline

16.2 g of 4-tert-butylbenzaldehyde and 3.0 g of acetone were added to afreshly prepared sodium methoxide solution and stirred at roomtemperature for 3 hours. It was washed with water and dried to obtainthe product bis (2-(4-tert-butyl) phenylvinyl) ketone. 7 g of bis(2-(4-tert-butyl) phenylvinyl) ketone and 2.2 g of phenylhydrazine werereacted in acetic acid for 4 hours. After cooling, the product waspurified to give 1-phenyl-3_(4-butylstyryl)-5-(4-tert-butylphenyl)pyrazoline, mp 192-197° C. UV-VIS (ETOH .max.) 387 nm.

Example 2 Synthesis of (I-2) Compound,1-phenyl-3-(p-methoxystyryl)-5-(p-methoxyphenyl)pyrazol

The same method as in Example 1, but replacing 4-tert-butylbenzaldehydewith p-methoxybenzaldehyde to obtain1-phenyl-3-(p-methoxystyryl)-5-(p-methoxyphenyl) Pyrazoline (I-2)compound, melting point 159° C. UV-VIS (ETOH .max.) 381 nm.

Example 3 Synthesis of a Compound of Formula (I-3),phenyl-3-(p-dimethylaminostyryl)-5-(p-dimethylaminophenyl) pyrazoline

The same method as in Example 1, but replacing 4-tert-butylbenzaldehydewith p-dimethylaminobenzaldehyde to obtainphenyl-3-(p-dimethylstyryl)-5-(p-dimethyl aminophenyl) pyrazoline,melting point 192° C., UV-VIS (ETOH.max.) 419 nm.

Example 4 Synthesis of Compound (II-1), dimethyl-2-(4-(dimethylamino)benzylidene) malonate

Dissolve 15 g of 4-(dimethylamino) benzaldehyde and 14.5 g of dimethylmalonate in dichloromethane and stir. Add molecular sieve to removewater and install a calcium chloride tube to prevent water. 1 ml ofpiperidine and 0.6 ml of acetic acid were added, and the reaction washeated at reflux temperature for 2 hours. Fresh molecular sieves wereadded during the reaction. After the reaction is completed, the solventis removed, and the dimethyl 2-(4-(dimethylamino) benzylidene) malonate(I-1) compound is obtained after acid washing and drying. The meltingpoint is 87-88° C. UV-VIS (CH₃CN max.) 384 nm.

Example 5 Synthesis of a Compound (II-2), ethyl2-ethyl-2-cyano-3-(4-(dimethylamino) phenyl) acrylate

The same method as in Example 4 except that ethyl 2-cyanoacetate wasused instead of dimethyl malonate to obtain ethyl2-ethyl-2-cyano-3-(4-(dimethylamino) phenyl) acrylate ester (II-2)compound, melting point: 125-126° C. UV-VIS (CH₃CN max.) 420 nm.

Example 6 Synthesis of the Compound (I-3), stearyl alkyl2-cyano-3-(4-(dimethylamino) phenyl) acrylate

24 g of compound II-2 was dissolved in toluene and heated at reflux in acondensing trap at 110° C. To the toluene solution were added 27 g ofstearyl alcohol and 1.5 g of p-toluenesulfonic acid. The reaction wasmonitored by HPLC. After the reaction was completed, it was dried byvacuum filtration to obtain compound (II-3). MS (M/Z: 468.4).

Example 7 Synthesis of a Compound of Formula (II-4),2-ethyl-2-cyano-3-(4-(dimethylamino) phenyl) acrylic acid polyetherester

The same method as in Example 6, Methoxypolyethylene glycol 350 was usedinstead of stearyl alcohol, and the product was purified by GPC toobtain 2-ethyl-2-cyano-3-(4-(dimethylamino) phenyl) acrylic acidpolyether ester (II-4) Compounds.

Example 8 Blue Light Blocking Composition and Film

150 g of butyl acrylate, 95 g of methyl methacrylate, 15 g of acrylicacid, 5.8 g of blue light blocking agent, and 6 g of benzoyl peroxidewere mixed in an ethyl acetate/toluene solvent, added to a reactionvessel, and heated to 75° C. After 2 hours, an additional of 6 g benzoylperoxide (in solvent) was slowly added dropwise, and the reactioncontinued for about 6 hours. The viscosity was monitored. After thereaction was completed, the temperature was lowered to room temperature.After coating on a PET film and removing the solvent by drying, a bluelight blocking film (100 gun) containing blue light blocking agent wasobtained. Measure the transmittance of blue light band at 400 nm. Theresults are shown in Table 1.

TABLE 1 Blue light transmittance of Example 8 Light transmittance % Bluelight (400 nm) blue light blocking agent transmittance % Ex. 8 blank,II-5 >80% Compound I-1, I-2, I-3, II-1, II-2 <20%

Example 9 Combination of Blue Light Blocking Agents

Table 2 shows the application of the compound of formula (I) alone, or acombination (I-1), (I-2), and (I-3), against blue light. Table 3 showsthe application of the compound of formula (II) alone, or a combinationof (II-1), (II-2), (II-5) against blue light. Table 4 shows theapplication of the combinations of (I-1), (II-1) and (II-5).

The “380-400 nm absorption” in Tables 2 to 4 indicates the absorption ofshorter wavelength blue light (higher energy). Basically, the greaterthe absorption, the better the protection against shorter wavelengths ofblue light will be. The “UVA1 & 380 nm-450 nm absorption” in Table 2indicates that it absorbs both long-wavelength UVA1 (about 340-400 nm)and blue light of 380 nm-450 nm, basically, the greater the absorption,the better the protection effect against long-wavelength ultravioletlight (UVA1) and full-band blue light. The “UVAB & 380 nm-450 nmabsorption” in Tables 3 and 4 indicates that it absorbs both UVAB (about290-400 nm) ultraviolet light and blue light in the full-band of 380nm-450 nm, the greater the absorption, the better the protection againstultraviolet (UVAB) and full-band blue light. In Tables 2 to 4, “410nm-450 nm absorption decreases” indicates that the absorption from 410nm to 450 nm decreases gradually and the transmitted blue light hasbetter color visual effects. “−” means poor effect, “+” means goodeffect, “++” means very good effect, and “+++” means excellent effect.

TABLE 2 Combinations of compounds of formula (I) 410-450 UVA1 & 380-400nm I-1 I-2 I-3 380-450 nm nm absorption (%) (%) (%) absorptionabsorption decrease 1 100  0 0 ++ +++ +++ 2 0 100  0 ++ +++ ++ 3 0 0100  ++ +++ ++ 4 0 40-60 40-60 +++ +++ ++ 5 40-60 40-60 0 ++ +++ +++ 640-60 0 40-60 +++ +++ ++ 7 30-40 30-40 30-40 +++ +++ ++

TABLE 3 Combinations of compounds of formula (II) 410-450 UVAB(290-400380-400 nm II-1 II-2 II-5 nm)& 380-450 nm absorption (%) (%) (%) nmabsorption absorption decrease 1 100  0 0 + +++ +++ 2 0 100  0 + +++ ++3 0 0 100  − − − 4 0 40-60 40-60 ++ +++ ++ 5 40-60 40-60 0 + +++ ++ 640-60 0 40-60 ++ +++ +++ 7 30-40 30-40 30-40 +++ +++ ++

TABLE 4 Combinations of formula (I) and formula (II) compounds 410-450UVAB & 380-400 nm I-1 II-1 II-5 380-450 nm nm absorption (%) (%) (%)absorption absorption decrease 1 40-60 40-60 0 + +++ +++ 2 30-40 30-4030-40 +++ +++ +++

The above embodiments are not to limit the scope of protection of thepresent invention. The various types of the present invention, as wellas technical solutions obtained by equivalent or equivalentsubstitutions, all fall within the protection scope of the presentinvention.

1. A blue light blocking system comprising at least one blue lightblocking film layer, and/or a basal layer, and/or one or more releasefilm layers, wherein the blue light blocking film layer is essential andincludes at least a compound selected from formula (I) and/or formula(II),

R₁ to R₃ are each independently selected from H, straight or branched C₁to C₆ alkyl, OR₃, and N(R₃)₂, R₄ to R₆ are each independently selectedfrom H, and straight or branched C₁ to C₆ alkyl, R₇ to R₈ are eachindependently selected from COOR₉, CONR₁₀R₁₁, COR₁₂, and CN, R₉ isselected from H, straight or branched C₁ to C₁₈ alkyl, and polyethyleneglycol groups, R₁₀ to R₁₂ are each independently selected from H,straight or branched C₁-C₆ alkyl, and phenyl.
 2. (canceled)
 3. The bluelight blocking system according to claim 1, wherein, the compound isselected from formula (I-1), (I-2), (I-3), (II-1) and (II-2):


4. The blue light blocking system according to claim 1, wherein thecompound of the formula (I) or formula (II) is used separately.
 5. Theblue light blocking system according to claim 1, wherein, the compoundof formula (I) and the compound of formula (II) are used in combination,and a mass ratio of the compounds ranges from 1:5 to 5:1.
 6. A bluelight blocking composition for preparing the blue light blocking layerof claim 1, comprising at least a compound selected from formula (I)and/or formula (II), and polymerizable monomers or polymers.
 7. The bluelight blocking composition according to claim 6, comprising at least acompound selected from formula (I) and/or formula (II), an initiator orinitiators, and polymerizable monomers and/or prepolymers.
 8. The bluelight blocking composition according to claim 6, wherein, the monomerincludes one or more acrylic, acrylic ester, methacrylic, methacrylicester, hydroxyacrylic, methacrylic, vinyl, styrene, diene, vinylfluoride, chlorine ethylene, acrylonitrile, vinyl acetate, siliconeacrylate, epoxy acrylate, polyurethane acrylate, ethylene oxide,isocyanate, polyol, polythiol, polyamine amine, alcohol amine, and thiolamine.
 9. The blue light blocking composition according to claim 6,further comprising one or more auxiliaries selected from stabilizer, UVabsorber, leveling agent, defoamer, dispersant, chain transfer agent,coupling agent, catalysts, toughener, tackifier, plasticizer, thickener,thinner, flame retardant, polymerization inhibitor, preservative,hardener, and acid-base blender.
 10. The blue light blocking compositionaccording to claim 6, wherein, a mass range of formula (I) or/andformula (II) is from 0.01% to 20%, a mass range of initiator content isfrom 0.01% to 10%, a mass range of monomer or prepolymer or polymercontent is from 5 to 99.98%.
 11. Use of a compound or a combination ofcompounds selected from the formula (I) and/or formula (II) according toclaim 1, for blocking blue light.